Subustituted phenyl alpha-(3-glutar-imidyl) acetates



United States Patent 3,391,144 SUBSTITUTED PHENYL a-(3-GLUTAR- IMIDYDACETATES Francis Johnson, Newton Lower Falls, Mass, assignor to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Original application Oct. 6, 1961, Ser. No. 144,011, now Patent No. 3,152,130, dated Oct. 6, 1964. Divided and this application Apr. 9, 1964, Ser. No.

'7 Claims. (Cl. 260-281) The present invention is directed to a process for preparing novel phenyl a-(3-glutarimidyl)acetate's. This application is a division of patent application Ser. No. 144,- 011, filed Oct. 6, 1961, now U.S. Patent 3,152,130.

It is an object of this invention to provide a process for preparing phenyl a-(3-glutarimidyl)acetates which are novel compounds usefiul in the preparation of actiphenols.

I discovered that an et-(3-glutarimidyl)acetyl halide may be reacted with a phenol in the presenece of a base, to prepare a phenyl e-(3-glutarin1idyl)acetate, as follows:

acetyl chloride is reacted with the phenol in the presence of a base (which acts as a scavenger for halide produced during the reaction), preferably a tertiary amine such as pyridine, to produce the corresponding phenyl oc-(3-gltltarimidyl)acetate. The acetate can be heated with AlCl and then cooled and hydrolyzed, to prepare 'actiphenols.

For the purpose of further explaining the invention to those skilled in the art, the following illustrative examples are given.

Example 1.-2,4-dimethylphenyl oc- 3+glutarimidyl) acetate a-(3-glutarimidyl)acetyl chloride (prepared from 5 g. of acid) was added to pyridine ('35 ml.). 2,4-dimethylphenol (5 g.) was added and the mixture warmed on a steam bath for 2 hours. At the end of this period the dark homogenous solution was added to methylene chloride (250 m1.) and water (250 ml). The mixture was filtered "ice to remove a small amount of black solid and the organic layer washed with 2 N hydrochloric acid (2X ml. portions). The methylene chloride abstract was then washed with water, with sodium carbonate solution and then with water, followed by drying over anhydrous magnesium sulphate. Brief boiling of this extract with charcoal followed by filtration removed most of the color associated with the liquid. The solution was then concentrated to small bulk on a water bath and other added to the point of spontaneous crystallization. Two crops of a highly crystalline white material were obtained of total weight, 6 g., M.P. -l556 C. A sample of the material was recrystallized at 4 times and had M.P. Found: C, 65.3; H, 6.0; N, 5.3. Required for: C H O N: C, 65.44; H, 6.22; N, 5.09%.

Example 2 Following the procedure of Example 1, 3,4dimethylphenol is used in place of the 2,4-dimethylphenol, to obtain 3,4-dimethylphenyl a-(B-glutarimidyl)acetate.

Example 3 Following the procedure of Example 1, 2,5dimethylphenol is used in place of the 2,4-dimethylphenol, to obtain 2,5-dimethylphenyl ot-(3-glutarimidyl)acetate.

Example 4 Following the procedure of Example 1, 2,4-diethylphenol is used in place of the 2,4-dimethylphenol, to obtain 2,4-diethylphenol or(3-glutarimidyl)acetate.

Example 5 Following the procedure of Example 1, 3,4-diethyl phenol is used in place of the 2,4-dimethylphenol to obtain 3,4-diethylphenyl a-(3 glutarimidyl)acetate.

Example 6 Following the procedure of Example 1, 2,5-diethylphenol is used in place of the 2,4-dimethylphenol, to ob tain 2,5-diethylphenyl ot(3-glutari.-midyl)acetate.

Example 7 Following the procedure of Example 1, 2-ohlorophenol is used in place of the 2,4-dime'thylphenol, to obtain 2-chl-or0phenyl a-( 3-glut-arimidyl) acetate.

Similarly, other phenyl a-(3-glutarinridyl) acetates are prepared from starting materials corresponding to the general definition wherein other substituent R groups on various ring carbons are varied. It appears that the substituents and side chains do not alter the condition of the reaction although the presence or absence of substituents on the ortho and para positions of the phenol influence the yield of the desired acetate.

The acetates are useful intermediates in the preparation of the actiphenols. The acetates exhibit anti-fungal activity. The acetate product of Example 1 was tested for control of tomato late blight. At 75 ppm, 40% control was attained and at 10 p.p.m., 20% control was attained. The actiphenols have shown themselves to have unusual biocidal activity and particularly outstanding activity as antifung al agents.

Although the invention has been illustrated by specific examples, it is to be understood that it includes all modifications and variations that come within the scope of the appended claims.

What is claimed is:

1. 2,4dimethylphenyl ot-(3-glutarimidyl)acetate.

2. '3,4-dimethylphenyl a-(3 glutarirnidyl) acetate.

3. 2,5-dimet hylp-henyl u-(3-glutarimidyl)acetate.

4. 2,4-die'thylphenyl a-(B-glutarimidyl)acetate.

3 4 5. 3,4-diethy1phenyl oc-( 3-glut-ari midy1)acetate. 3,067,092! 12/1962 Feichtinger et a1. ,167-22 6. 2,5-diethy1pheny1 a (3-g1utari1midy1)acetate. 3,108,036 10/ 1963 Molvar 167-22 7. 2-ch10ropheny1-a- 3-glutarirnidyl acetate.

OTHER REFERENCES References Cited 5 Lucas Organic Chemistry, 2nd Ed., American Book Co. UNITED STATES PATENTS 2,717,126 8/1955 Mulvaney NICHOLAS RIZZO, Primary Emmmeh 3,076,809 2/ 1963 Johnson 260-281 D. G. DAUS, Assistant Examiner. 

5. 3,4-DIETHYLPHENYL A-(3-GLUTARIMIDYL) ACETATE. 